Polyester fibers dyed with monoazo compounds

ABSTRACT

Polyester fibers are dyed bright, fast yellow to blue shades with a monoazo compound containing a substituted phenyl diazo component and an N,N-di-aralkyl-m-acylamidoaniline coupling component.

United States Patent [1 1 Weaver et al.

[ Oct. 16, 1973 POLYESTER FIBERS DYED WITH MONOAZO COMPOUNDS [75]Inventors: Max A Weaver; Herman S. Pridgen,

both of Kingsport, Tenn.

[73] Assignee: Eastman Kodak Company,

Rochester, NY.

[22] Filed: Jan. 4, 1972 [21] Appl. No.: 215,400

Related U.S. Application Data [62] Division of Ser. No. 728,788, May 13,1968.

[52] U.S. Cl 8/41 C [51] Int. Cl C09b 27/00 [58] Field of Search 8/41 A,41 B, 41 C;

Primary ExaminerDonald Levy Attorney-Cecil D. Quillen, Jr. et al.

[5 7] ABSTRACT Polyester fibers are dyed bright, fast yellow to blueshades with a monoazo compound containing a substituted phenyl diazocomponent and an N ,N-di-aralkylm-acylamidoaniline coupling component.

12 Claims, No Drawings wherein R is a substituted phenyl group;

R is an acyl group;

R is hydrogen, lower alkyl, or-lower alkoxy;

R and R are the same or different and each is alkylene of l to about 2carbon atoms; and

R and R are the same and each is hydrogen, lower alkyl, lower alkoxy orhalogen.

When applied to polyester textile materials according to conventionaldyeing procedures, the compounds of the invention exhibit improvedbuild-up, excellent brightness, and superior fastness properties, suchas fastness to light and resistance to sublimation. The novel azocompounds impart various shades, ranging from yellow to blue, topolyester fibers. The improved fastness properties possessed by thenovel azo compounds allows them to be employed in the dyeing ofcotton-polyester fabrics receiving durable press processing. Thesuperior sublimation fastness possessed by the compounds of theinvention renders them particularly useful in the thermal fixationtechnique of dyeing polyester materials.

Examples of the substituents present on the phenyl group represented byR include nitro, halogen, lower alkylsulfonyl, formyl, lower alkanoyl,lower alkoxycarbonyl, cyano, trifluoromethyl, sulfamoyl, loweralkylsulfamoyl, carbamoyl, lower alkylcarbamoyl, thiocyanato, etc. Asused herein to describe a group containing an alkyl moiety, lowerdesignates a carbon content from one to about four carbon atoms. Thealkanoyl groups can be substituted with substituents such as halogen,phenyl, cyano, lower alkoxy, hydroxy, lower alkylsulfonyl, phenyl, etc.The alkylsulfonyl groups can also be substituted, for example, withcyano, hydroxy, halogen and the like. Typical of the groups, containingan alkyl moiety, which can be present on phenyl radical R aremethylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, acetyl,propionyl, isobutyryl, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl,dimethylsulfamoyl, ethylsulfamoyl, propylsulfamoyl, dibutylsulfamoyl,methylcarbamoyl, diethylcarbamoyl, butylcarbamoyl, etc. Chlorine andbromine are typical halogen atoms which can be present on phe nylradical R.

Illustrative of the phenyl groups which R can represent are2-chloro-4-nitrophenyl, 4-nitrophenyl, 2-chloro-4-methylsulfonyl,2,4-di(methylsulfonyl)phenyl, 2-methylsulfonyl-4-nitrophenyl,2-nitro-4-methylsulfonylphenyl, 2-acetyl-4-nitrophenyl,2-ethoxycarbonyl-4-nitrophenyl, 2,4-dinitro-6-chlorophenyl,2-cyano-4,6-dinitrophenyl, 4-methoxycarbonylphenyl,2-ethylsulfonyl-4,6-dinitrophenyl, 2-formyl-4,6- dinitrophenyl,2,4-dinitro-6-propionylphenyl, 2- ethoxycarbonyl-4,6-dinitrophenyl,2-trifluoromethyl-4- nitrophenyl, 2,4-dicyanophenyl, 2-bromo-6-cyano-4-nitrophenyl, 4-nitro-2-sulfamoylphenyl, 2-nitro-4-(dimethyl)sulfamoylphenyl, 4-cyanophenyl, 4-methylsulfonylphenyl,4-trifluorornethylphenyl, 4- chlorophenyl, 4-ethylsulfamoylphenyl,4-acetylphenyl, 4-ethylcarbamoylphenyl, 2-carbamoyl-4-nitrophenyl,2-methylsulfonyl-4-thiocyanophenyl, 2,6-dichloro-4- nitrophenyl,Z-nitro-4-thiocyanatophenyl, 2-chloro-6- cyano-4-nitrophenyl,2-cyano-4-nitrophenyl, 2-chloro- 4-cyanophenyl,2-chloro-4-ethoxycarbonylphenyl, and the like. Preferably, thesubstituted phenyl group R contains not more than three substituents atthe para and ortho positions.

The acyl groups represented by R can be formyl, lower alkanoyl, aroyl,cyclohexylcarbonyl, lower'alkoxycarbonyl, aryloxycarbonyl, loweralkylsulfonyl, arylsulfonyl, carbamoyl, loweralkylcarbamoyharylcarbamoyl, furoyl, etc. The alkanoyl and alkylsulfonylgroups can be substituted as described above in the definition of R.Acetyl, propionyl, butyryl, cyanoacetyl, chloroacetyl, phenylacetyl,methoxyacetyl, methylthioacetyl, methylsulfonylacetyl, methoxycarbonyl,propoxycarbonyl, butoxycarbonyl, methylsulfonyl, ethylsulfonyl,propylsulfonyl, butylsulfonyl, 2-cyanoethylsulfonyl,2-hydroxyethylsulfonyl, and 2-chloroethylsulfonyl are examples of thealkanoyl, alkoxycarbonyl, and alkylsulfonyl groups which R canrepresent. The aryl group of the aroyl, aryloxycarbonyl, arylsulfonyl,and arylcarbamoyl group is preferably monocyclic, carbocyclic aryl suchas unsubstituted phenyl and phenyl substituted with, for example, loweralkyl, lower alkoxy, halogen, hydroxy, etc. Tolyl, anisyl, pbromophenyl,and o,p-dichlorophenyl are typical of such aryl groups.Dimethylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, and butylcarbamoylare illustrative alkylcarbamoyl groups which R can represent.

Methylene, ethylene, methyl, ethyl, propyl, butyl, methoxy, ethoxy,butoxy, chlorine, and bromine are examples of the substituents whicheach of R", R, R and R, as defined above, can represent.

Particularly good dyeings on polyester materials are obtained byapplying to such materials a compound of group A or group B describedbelow.

wherein R is 2-chloro-4,6-dinitrophenyl, 2bromo-4,6- dinitrophenyl,2-formyl-4,6-dinitrophenyl, 2-lower alkanoyl-4,6-dinitrophenyl,2-lower-alkoxycarbonyl- 4,6-dinitrophenyl, or2-trifluoro-4,-dinitrophenyl;

R is lower alkanoyl, benzoyl, lower alkylsulfonyl, lower alkoxycarbonyl,or lower alkylcarbamoyl;

R is methoxy or ethoxy; and

R and R each is hydrogen, methyl, methoxy, or chlorine.

wherein R is 2-chloro-4nitrophenyl, 2-bromo-4-nitrophenyl,4-nitrophenyl, 2-chloro-4-lower alkylsulfonylphenyl, 2-bromo-4-loweralkylsulfonylphenyl, 2,4-di(lower alkylsulfonyD-phenyl, 2-loweralkylsulfonyl-4- nitrophenyl, 2-lower alkylsulfonyl-4-thiocyanatophenyl, 2-cyano-4,6-dinitrophenyl, trifluoromethyl-4nitrophenyl, 2-chloro-6-cyano-4- nitrophenyl, 2bromo-6-cyano-4-nitrophenyl, or 4- lower alkylsulfonylphenyl;

R is lower alkanoyl, benzoyl, lower alkylsulfonyl, lower alkoxycarbonyl,or lower alkylcarbamoyl; and

R and R each is hydrogen, methyl, methoxy or chlorine.

The compounds of group B wherein R is 2-chloro-4- nitrophenyl;2-bromo-4-nitrophenyl, 2-chloro-4-lower alkylsulfonylphenyl,2-bromo-4lower alkylsulfonylphenyl, 2,4-di(lower alkylsulfonyhphenyl,2-lower alkylsulfonyl-4-nitrophenyl, or, especially, 2-cyano-4,6-dinitrophenyl exhibit exceptional fastness properties when appliedto polyester fibers.

The novel azo compounds of the invention are prepared according to knownprocedures by diazotizing an (Ill) NHR amine having the formula R'NHgand coupling the resulting diazonium salt with a compound having theformula wherein R, R R, R, 'R, R and R are defined above. The amines R-NH, are known compounds and can be prepared by published techniques. 1

The coupler compound of formula (II) are prepared in accordance withanalagous procedures described in the literature. The couplers can beprepared by reacting a compound having the formula (III) l Q-NHLQ NHR(IV) i NHR wherein X is halogen. The compounds of formula IV can beprepared by condensing a benzaldehyde or arylacetaldehyde with amine lllfollowed by hydrogenation of the resulting anil. The above-describedsynthesis of the couplers can be varied by substituting a nitroanilinehaving the formula I Ewe lL A for amine (111). The nitro group of theintermediate N,N-disubstituted nitroaniline is hydrogenated and theresulting amino group is acylated.

The preparation of the couplers and representative azo compounds of theinvention is further illustrated by the following examples.

PREPARATION OF THE COUPLERS Example 1 A mixture of 15.0 g.3'-aminoacetanilide, 38.0 g.

benzylchloride, and 25 m1. N,N-dimethylformamide are heated and stirredfor 2 hr. at9S-l05 C. Then 10.1 g. triethylamine is added, and thereaction is heated for another hour at l -125 C. After drowning thereaction in water, the product, 3-acetamido- N,N-dibenzylaniline, iscollected by filtration, washed with water, and air dried; m.p. 140-142C.

Example 2 A mixture of 15.0 g. 3'-aminoacetanilide, 12.7 g.

benzyl chloride, and25 ml. N,N-dimethylformamide are heated for 12minutes at 60-65 C. and then drowned in 350 ml. water. The product iscollected by filtration and recrystallized from 250 ml. of benzene and60 ml. of hexane. The product obtained, 3-acetamido-N-benzylaniline,melts at 129130 C. Example 3 A mixture of 18.0 g. 3'-nitroacetanilide,2.0 g. sodium acetate, 31.8 g. benzaldehyde, 150 ml. ethanol, and 3 g.Raney nickel is hydrogenated at 75 C. and 1,500 psi. until the hydrogenuptake ceases. Ethanol (100 ml.) is added to the product from theautoclave. After heating to dissolve the product, the Raney nickel isremoved by filtration. After removing most of the solvent byevaporation, the residue is poured into wa-- ter. The product iscollected by filtration, washed with water, and air dried. it melts atl28130 C. and is identical to that prepared by the procedure of Example2. Example 4 3'-Aminoacetanilide (15.0 g.), 2- phenylethylbromide (18.5g.) and N,N-dimethylformamide (25 ml.) are heated at 80 C. for 1.25 hr.The reaction mixture is drowned into water. The slightly gummy product,3-acetamido-N-(2- phenylethyl)aniline, is collected by filtration andair dried. Example 5 A mixture of 3-acetamido-N-(2-phenylethyl)aniline(2.5 g.), benzylchloride (2.6 g.), and N,N-dimethylformamide (3.0 ml.)are heated at 95 C. for 0.5 hr. Triethylamine (2 g.) is added and theheating continued for 0.5 hour. The reaction is drowned into water. Theproduct, 3-acetamido-N-benzyl-N-(2- phenylethyl)aniline, is washed bydecantation; it is a light amber viscous material.

Example 6 3'-Aminoacetanilide (8.0 g.), a-chloro-p-xylene (21.0 g.), andml. N,N-dimethylformamide are heated at 95 C. for 1.5 hr. with stirring.Then 25 ml. of .triethylamine is added and heating continued 7 hr.longer. The reaction mixture is drowned into water, and the productcollected by filtration, washed with water, and air dried. The product,3-acetamido-N,N- (di-p-methylbenzyl)aniline, melts at l6l-l62 C. Example7 A mixture of 5-acetamido-2-methoxyaniline (18.0 g.), benzyl chloride(38.0 g.), and N,N-dimethylformamide are heated and stirred at 95 C. for1 hr. Then triethylamine (26 ml.) is added, and the reaction is heated 2hr. longer. After drowning in water, the product is collected byfiltration and recrystallized from 250 ml. methanol plus a little water.The product, 5- acetamido-N,N-dibenzyl-2-methoxyaniline, melts atl38-139.5 C.

Example 8 m-Nitroaniline (69.0 g.), benzyl chloride (133.0 g.), andN,N-dimethylformamide (250 ml.) are heated at 130 C. for 6 hr. Thereaction mixture is drowned in a hot water-methanol solution; theproduct crystallizes on stirring. After collection of the product byfiltration, it is recrystallized from methanol to give 129 g. of yellowsolid, N,N-dibenzyl-3-nitroaniline, which melts at 78-80 C.N,N-dibenzyl-3-nitroani1ine (129 g.) is hydrogenated in 800 ml. of2Balcohol using Raney nickel catalyst (14.0 g.). The reaction is carriedout at 75 C. and at 1,500 psi. and requires about 3 hr. The Raney nickelcatalyst is then removed by filtration. Upon concentration of thefiltrate to about one-third of the original volume, the productseparates and is collected by filtration and dried in air. The yield is103 g. of N,N- dibenzyl-m-phenylenediamine melting at 98-100 C. Example9 g v N,N-Dibenzyl-m-pheny1enediamine (14.4 g.), toluene (30.0 ml.), andpropionic anhydride (5.0 ml.) are heated at 95-100 C. for 3 hr. withstirring. The reaction mixture is drowned with hexane, and the productis collected by filtration. It is recrystallized from a 3:1benzene/hexane solution. The yield is 11.3 g. of N ,N-dibenzyl-3-propionamidoaniline melting at l33134 C. Anal. Calcd. for C HN oz C, 80.2; H, 7.04; N, 8.13. Found: C, 80.35; H, 6.97; 7.83. Example10 N,N-Dibenzyl-m-phenylenediamine (8.64 g.), toluene (20.0 ml.) andformic acid (3.0 ml.) are heated at 95100 C. for 4 hr., and then thereaction mixture is drowned in a water/methanol mixture. The product,

.ethoxyformamidoaniline, crystallizes on stirring and is collected byfiltration. Example 12 To a solution of 8.64 g. of N,N-dibenzyl-mphenylenediamine in 20 ml. of pyridine is added 4.0 g. ofmethanesulfonyl chloride. After stirring at 95100 C. for 2 hr., thereaction is drowned in 600 ml. of dilute HCl solution. The aqueousportion is decanted and the product recrystallized from ethanol to yield3- methanesulfonamido-N,N-dibenzylaniline melting at l 13-1 14 C.

Example 13 To a solution of N,N-diben2yl-m-phenylenediamine (5.76 g.) indioxane (15.0 ml.) is added ptoluenesulfonyl chloride (4.75 g.). Thereaction is? heated on a steam bath for 2 hr. and then is drowned inwater. The product crystallizes and then is collectedi by filtration.After recrystallizing from methanol the product,3-(p-toluenesulfonamido)-N,N- dibenzylaniline, melts at 134l35 C. IExample 14 To a solution of N,N-dibenzyl-m-phenylenediamine; (8.64 g.)in toluene (20 ml.) is added ethyl isocyanate (2.12 g.). The reactionmixture is heated on a steam bath for 30 min. On cooling the productcrystallizesi and is collected by filtration. The product, N,N-idibenzyl-3-(3-ethy1ureido)aniline, is recrystallized" from amethanol-water solution and melts at 1S4-l 57 1 C. Anal. Calcd. for CI-1 19 C, 77.0; H, 6.76; N, 11.7. Found: C, 77.0; H, 6.5; N, 11.6.Example 15 To a solution of N,N-dibenzylm-phenylenediamine (8.64 g.) in15 ml. otdioxane is added 2-furoyl chloride (4.3 g.). The reaction isheated with stirring on a steam bath for 15 min. and then is drowned inwater. The aqueous portion is removed by decantation and the product isrecrystallized from methanol. The product,N,N-dibenzyl-3-(2-furoylamido)aniline, melts 145-148 C. Anal. Calcd. forC d-1 N 0 C, 78.5; H,: 5.8; N, 7.3. Found: C, 78.3; H, 5.4; N, 6.9.Example 16 3-Cyclohexylformarnidoaniline (10.9 g.), benzyl chloride(13.35 g.), and N,N-dimethylformamide (25 3'-Aminobenzanilide (10.6 g.)is reactedwith benzyl chloride (13.35 g.) exactly as in'Example 16 togive 3- (benzamido)N,N-dibenzylaniline, which melts at 169-171 C.Example 18 3-Aminoacetanilide (7.5 g.), p-chlorobenzyl chloride (24.2g.), and N,N-dimethylformamide (25.0 ml.) are heated on a steambath for4 hr.; during this time 10 ml. of triethylamine is added portionwise.The reaction mixture is drowned in 600 ml. water plus ml. of methanol.It is collected by filtration, dried in air, and recrystallized from abenzene-hexane solution. The yield is 19.7 g. of3-acetamido-N,N-bis(pchlorobenzyl)-aniline which melts at l74-l77 C.Example 19 Z-Methoxy-S-acetamidoaniline (9.0 g.), N,N-dimethylformamide(15 ml.), and p-chlorobenzyl chloride (24.2 g.) are heated on a steambath for 1 hr. Triethylamine (25 ml.) is added and the reaction heated 3hr. longer. It is then drowned in water and recrystallized from abenzene-hexane solution. The yield is 20.8 g. ofS-acetamido-N,N-bis(p-chlorobenzyl)-2- methoxyaniline which melts at153-158 C. Anal. Calcd. for (3,,H,,C1,N,0, C, 64.4; H, 5.2; N, 6.5; Cl,16.5. Found: C, 64.6, H, 5.5; N, 6.4; Cl, 6.5. Example 205-Acetamido-2-methoxyaniline (9.0 g.), N,N-dimethylformamide (15 ml.),p-methylbenzylchloride (17.5 g.), and 25 ml. of triethylamine arereacted as illustrated by Example 19 to yield5-acetamido-N,N-bis(pmethylbenzyl)-2-methoxyaniline which melts at185-l87 C. Example 21 5-Acetamino-2-methylaniline (16.4 g.),N-N-dimethylformamide (50.0 ml.), and benzyl'chloride (37.8 g.) areheated at 1 10 C. for 8 hr. The product is collected by filtration,washed with water, and recrystallized from 200 m1. of methanol. Theproduct, S-acetamido- N,N-dibenzyl-Z-methylaniline, melts at 181-l82 C.Anal. Calcd. for C H N O: C, 75.3; H, 7.1; N, 11.0.

Found: C, 75.7; H, 7.0; N, 10.9.

PREPARATION OF THE AZO COMPOUNDS 2 Example 22 To 5 m1. conc. H is added0.72 g. of NaNO with stirring. This solution is cooled and 10 ml. 1:5acid (1 part propionic acid:5 parts acetic acid) is added below 10C.'This is stirred and 1.72 g. 2-chlo ro-4-nitroaniline is addedfollowed by 10 ml. additional 1:5 acid, all at 5 C. The diazotization isstirred at 0-5 C. for 3 hr. and then added to a chilled solution of 3.30g. 3- acetamido-N,N-dibenzylaniline dissolved in ml. of 1:5 acid. Thecoupling is kept cold (below 5 C.) and buffered with solid ammoniumacetate until neutral to Congo Red paper. After allowing to couple for 2hr., the product is drowned in water, collected by filtration, washedwith water and dried in air. The azo compound produces bright red shadeson polyester fibers and has Example 23 v 2,4-Bis(methylsulfonyl)aniline(2.49 g.) is diazotized and coupled to 3-acetamido-N,N-dibenzylaniline(3.30 g.) by using diazotization and coupling procedures given inExample 22 to yield the azo compound 4-(2,4- dimethylsulfonylphenylazo)-N,N-dibenzyl-3- acetamidoaniline. This compound produces brilliant redshades on polyester fibers.

Example 24 2-Methylsulfony1-4-nitroaniline is diazotized and coupledwith 3-acetamido-N,N-bis(p-rnethylbenzyl- )aniline as described inExample 22 to yield the following dye'4-(2-methylsulfonyl-4-nitrophenylazo)-N,N dibenzyl-3-acetamidoanilinewhich imparts deep violet shades, having excellent fastness, topolyester fibers. Example 25 p-Nitroaniline (6.9 g.) is dissolved in 5.4ml. conc. H 50, and 12.6 ml. water. This solution is poured on 50 g. ofcrushed ice, and then a solution of 3.6 g. NaNO in 8 ml. water is addedall at once. The diazotization is stirred at 0-5 C. for 1 hr., and thenthe solution is added to a chilled solution of 3-acetamido-N,N-dibenzylaniline (16.5 g.) dissolved in 250 ml. of 1:5 acid. The couplingis kept at 0-5 C. and neutralized with ammonium acetate until it isneutral to Congo Red paper. After coupling 2 hr., the mixture is drownedin water. The product is collected by filtration, washed with water, andair dried. It has the following structure: Q NH 5 2 cmQ (Y). OQN -N=N N\Q NHCOCH:

This compound produces bright scarlet shades on polyester fibers.

The azo compounds described in the examples of the scribed in Examples22 and 25 by diazotizing 0.01 mole of an amine having the formulawherein Y is a substituent and n is 1, 2 or 3, and coupling theresulting diazonium with 0.01 mole of a compound of formula (II). Theazo compounds of the table conform to formula (I) in which R correspondsto the phenyl group of the above amine. The color given for each of thecompounds refers to dyeings on polyester COCH;

The compounds of the invention can be used for dyeing linear polyestertextile materials in the manner described in U.S. Pat. Nos. 2,880,050,2,757,064, 2,782,187 and 3,043,827. The following example illustrates acarrier dyeing procedure for applying the 2120 compounds of theinventionto dye polyester textile materials.

Example 161 An amount of 0.1 g. of the azo compound is dissolved in cc.of Z-methoxyethanol. A small amount (3-5 cc.) of a 3% sodium ligninsulfonate aqueous solution is added, with stirring, and then the volumeof the bath is brought to 300 cc. with water. 3 cc. of an anionicsolvent carrier (Tanavol) is added to the bath and 10 The compounds ofthe invention can also be applied to polyester textile materials by theheat fixation technique described in US. Pat. No. 2,663,612 and in theAmerican Dyestuff Reporter, 42, 1 (1953 The following proceduredescribes how the azo compounds of the invention can be applied topolyestermaterials by the heat fixation technique.

Example 162 A mixture of:

500 mg. of an azo compound of the above Example, 150 mg. of a sodiumlignosulfonate dispersing agent (Marasperse N), 150 mg; of a partiallydesulfonated sodium lignosulfonate (Marasperse CB), 0.5 ml. glycerin,and 1.0 ml. of water is ground in a microsize container (an accessoryfor a l-quart size Szegvari Attritor) for approximately 3.5 hours.Enough 1/8-inch stainless steel balls are added to provide maximumgrinding. When the grinding is complete, the entire contents are pouredinto a beaker and ml. of water are used to wash the remaining dye pastefrom the microcontainer. The dye paste is then heated slowly to 65 C.with continuous stirring.

A thickener and penetrating mixture is prepared by mixing 1 ml. of acomplex diaryl sulfonate surfactant, (compound 8-8),

3 ml. of a 3% solution of a sodium N-methyl-N- oleoyltaurate (lgepon T-Sl 8.ml. of a 25% solution of natural gums (Superclear SON), andsufficient water to bring the volume to 100 ml. The thickener andpenetrating mixture is added to the dye paste, the volume is adjusted to200 ml. and the mixture is agitated for 15 minutes. The dye mixture isthen filtered through folded cheesecloth to remove the stainless steelballs and it then is added to the resevoir of a Butterworth padder whereit is heated to about 4560 C.

10 g. of a fabric of poly(ethylene terephthalate) fibers and 10 g. of afabric of 65/35 spun poly(ethylene terephthalate)/cotton fibers are sewntogether, end-toend, and padded for minutes of continuous cyclingthrough the dye mixture and between three rubber squeeze rollers of thepadder. Dye mixture pick-up is about 60% based on the weight of thefabrics.

The padded fabrics are then dried at 200 F. and then heat-fixed for 2minutes at 415 F. in a forced air oven.

The dyed fabrics are scoured for 20 minutes at 6570 The heat fixationdyeing procedure described above can be varied by the substitution ofother dispersing agents, surfactants, suspending agents, thickeners,etc. The temperature and time of the heat-fixation step can also bevaried.

Polymeric linear polyester materials of the terephthalate sold under thetrademarks Kodel'fl Dacron" and Terylene are illustrative of thelineararomatic polyester textile materials that can be dyed with thecompounds of our invention. Examples of linear polyester textilematerials that can be dyed with the compounds of the invention are thoseprepared from ethylene glycol and dimethylterephthalate or fromcyclohexanedimethanol and dimethylterephthalate. Polyesters preparedfrom cyclohexanedimethanol and dimethylterephthalate are moreparticularly described in U.S. Pat. No. 2,901,446. Poly(ethyleneterephthalate) polyester fibers are described, for example, in U.S. Pat.No. 2,465,319. The polymeric linear polyester materials disclosed inU.S. Pat. Nos. 2,945,010, 2,957,745, and 2,989,363, for example, can bedyed. The linear aromatic polyester materials specifically named have amelting point of at least 200 C. The poly(ethylene terephthalate) fiberswhich are dyed with the compounds of the invention are manufactured froma melt of a polymer having an inherent viscosity of at least 0.35 andpreferably, about 0.6. The inherent viscosity of thepoly(l,4-cyclohexylenedimethylene terephthalate) polymer is also atleast 0.35. These inherent viscosities are measured at 25 C. using 0.25g. polymer per 100 ml. of a solvent consisting of 60% phenol and 40%tetrachloroethane. The polyester fabrics, yarns, fibers and filamentsthat are dyed with the novel azo compounds can also contain minoramounts of other additives such as brighteners, pigments, delusterants,inhibitors, stabilizers, etc.

The invention has been described in considerable detail with particularreference to preferred embodiments thereof, but it will be understoodthat variations and modifications can be effected within the spirit and5 scope of the invention as described hereinabove and as defined in theappended claims.

We claim: 1. A fiber having a basis of a linear terephthalate polyesterdyed with an azo compound having the formula wherein R is phenylsubstituted with 1, 2 or 3 groups selected from the class consisting ofnitro, halogen, lower alkylsulfonyl, lower cyanoalkylsulfonyl, lower.hydroxyalkylsulfonyl, lower haloalkylsulfonyl, formyl, lower alkanoyl,lower cyanoalkanoyl, lower alkoxyalkanoyl, lower hydroxyalkanoyl, loweralkylsulfonylalkanoyl, lower alkoxycarbonyl, cyano, trifluoromethyl,sulfamoyl, lower alkylsulfamoyl, di-lower alkylsulfamyl, carbamoyl,di-lower alkylcarbamoyl, or thiocyanato;

R is formyl, lower alkanoyl, lower cyanoalkanoyl, lower alkoxyalkanoyl,lower hydroxyalkanoyl, lower alkylsulfonylalkanoyl, lowerphenylalkanoyl, benzoyl, lower alkylbenzoyl, lower alkoxybenzoyl,halobenzoyl, cyclohexylcarbonyl, lower alkoxycarbonyl, phenoxycarbonyl,lower alkylphenoxycarbonyl, lower alkoxyphenoxycarbonyl,halophenoxycarbonyl, lower alkylsulfonyl, lower cyanoalkylsulfonyl,lower hydroxyalkylsulfonyl, lower haloalkylsulfonyl, phenylsulfonyl,lower alkylphenylsulfonyl, lower alkoxyphenylsulfonyl,halophenylsulfonyl, carbamoyl, lower alkylcarbamoyl di-loweralkylcarbamoyl, phenylcarbamoyl, lower alkylphenylcarbamoyl, loweralkoxyphenylcar- I bamoyl, halophenylcarbamoyl or furoyl;

R is hydrogen, lower alkyl or lower alkoxy;

R and R are the same or different-and each is alkylene of about 1 to 2carbon atoms; and l R and R are the same or different and each ishydrogen, lower alkyl, lower -alkoxy or halogen.

50 2. A fiber according to claim 1 wherein the polyester ispoly(ethylene terephthalate) or poly( 1,4- cyclohexylene dimethyleneterephthalate).

3. A fiber according to claim 2 wherein the azo compound has theformula:

R is methoxy or ethoxy; and

R and R are the same or different and each is hydrogen, methyl, methoxy,or chlorine.

4. A fiber according to claim 2 wherein the azo com- 8. A fiberaccording to claim 2 wherein the azo compound has the formula pound hasthe formula l NHRI 10 9. A fiber according to claim 2 wherein the azocomwh i pound has the formula R is 2-chloro-4-nitrophenyl,2-bromo-4-nitrophenyl,

4-nitrophenyl, 2-chloro-4-lower alkylsulfonylphe- N02- nyl,2-bromo-4-lower alkylsulfonylphenyl, 2, 4-di- CHrloweralkylsulfonylphenyl, 2-lower alkylsulfonyl-4- 02NN= N nitrophenyl,2-lower alkylsulfonyl-4- I thiocyanatophenyl, 2-cyano-4,6-dinitrophenyl,2- N OCH: trifluoromethyl-4-nitrophenyl, 2-chloro-6-cyano-4- mtrophenyl2'bromo'6'cyano'4'nmophenyl or 10. A fiber according to claim 2 whereinthe azo R and R are the same or different and each is hydrogen, methyl,methoxy or chlorine. 5. A fiber according to claim 4 wherein R is2-chloro- 4-nitrophenyl, 2-bromo4-nitrophenyl, 2-chloro-4 OZN loweralkylsulfonyl, 2-bromo-4-lower alkylsulfonylphel 1 Uni-Q nyl,2,4-di-lower alkylsulfonylphenyl, 2-lower all:ylsulfonyl-4-nitrophenylor 2-cyano-4,6- dinitrophenyl. 11. A fiber according to claim 2 whereinthe azo 6. A fiber according to claim 2 wherein the aim comcompound hasthe formula pound has the formula 0m N='N N cmQ 1 NHCOCH3 I CH2 1NHCOCH;

12. A fiber according toclaim 2 wherein the azo 40 compound has theformula 7. A fiber according to claim 2 wherein the azo compound has theformula 0 0cm CH:

0,N 'N. N N/ C NHCOCH; OzN -N=N-N V l 2- SO CH; NHCOCI-la 1|: a

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3,765,830 DatedOctober 16.. 1973 It is certified that error appears in theabove-identified patent and that said Letters Patent are hereby'corrected as shown below:

/"K \t NHR (III) 2 1 Q m 2 r 0 o h. M

m I t//.\ 4 w e e 6 I l e 6 6 e l w c h u n n 1., 2 1 R Q o R w... R mFm n m a g M m n 1 .1 d d d a n m h a .h n e .m 5 S h t X w t r o o 4 ae F a 6 d m a n u //4\ .mo u u a 5 I 9- 2- n m n0 e x 1 e e 2 e 5. m m;l 2 3 4 H k 2 k m e n u o e e 2 1 l l l OR 0 t :H a ar a 0 o N 8 T n c Tw I e e w m m m m m C E8 E8 Patent No.

lnvemods) Max A. Weaver and Herman S. Pridgen Column 4, line 17 delete"compound" andinsert --compounds-.

Column 4, line 41 to bottom of column, delete the entire formula andinsert therefor P ggso UNITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION patemNo 3,765,830 Dated October 16. 1973 Inventods) Max A.Weaver and Herman S. Pridgen It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

[- Column 12, line 53,-delete "Example" and insert Examples-.

Column 15, Claim 4, delete the formula therein and insert Signed andsealed this 30th day of April 19714..

(SEAL) Attest:

EDWARD I-LFLETCEERJR. C. MARSHALL DANN Attesting Officer Commissioner ofPatents

2. A fiber according to claim 1 wherein the polyester is poly(ethylene terephthalate) or poly(1,4-cyclohexylene dimethylene terephthalate).
 3. A fiber according to claim 2 wherein the azo compound has the formula:
 4. A fiber according to claim 2 wherein the azo compound has the formula
 5. A fiber according to claim 4 wherein R is 2-chloro-4-nitrophenyl, 2-bromo-4-nitrophenyl, 2-chloro-4-lower alkylsulfonyl, 2-bromo-4-lower alkylsulfonylphenyl, 2,4-di-lower alkylsulfonylphenyl, 2-lower alkylsulfonyl-4-nitrophenyl or 2-cyano-4,6-dinitrophenyl.
 6. A fiber according to claim 2 wherein the azo compound has the formula
 7. A fiber according to claim 2 wherein the azo compound has the formula
 8. A fiber according to claim 2 wherein the azo compound has the formula
 9. A fiber according to claim 2 wherein the azo compound has the formula
 10. A fiber according to claim 2 wherein the azo compound has the formula
 11. A fiber according to claim 2 wherein the azo compound has the formula
 12. A fiber according to claim 2 wherein the azo compound has the formula 